JP2017514956A - Amphiphilic block copolymers; compositions, membranes, and separation modules thereof; and methods for making the same - Google Patents

Abstract

The amphiphilic block copolymer comprises a poly (phenylene ether) block or poly (phenylene ether) copolymer block and a hydrophilic block or graft. A method for producing an amphiphilic block copolymer comprises polymerizing a hydrophilic ethylenically unsaturated monomer in the presence of poly (phenylene ether) or poly (phenylene ether) copolymer to produce an amphiphilic block copolymer. . A porous asymmetric membrane comprises a poly (phenylene ether) or poly (phenylene ether) copolymer and an amphiphilic block copolymer comprising a poly (phenylene ether) block or poly (phenylene ether) copolymer block and a hydrophilic block or graft. Including. Porous asymmetric membranes are produced by phase transformation in a coagulation bath of a dope solution of poly (phenylene ether) or poly (phenylene ether) copolymer and amphiphilic block copolymer.

Description

  It relates to the technology of amphiphilic block copolymers.

  Poly (phenylene ether) is a plastic having excellent water resistance, heat resistance, and dimensional stability. They retain their mechanical strength in high temperature and / or high humidity environments. They can therefore be used to make porous asymmetric membranes useful in various separation processes. For example, poly (phenylene ether) can be used in processes that require repeated washing with hot water or steam sterilization. However, the use of poly (phenylene ether) in various water treatment processes can be limited due to their hydrophobic nature. The membrane cannot be wetted by water and a high pressure gradient is required to pass water through the pores of the membrane. Furthermore, hydrophobic interactions between the membrane and the feed stream solute can cause membrane fouling, which adversely affects membrane performance and requires cleaning or membrane replacement.

US Pat. No. 3,703,564

  The surface of a membrane made from a hydrophobic polymer can be made hydrophilic by blending with a hydrophilic polymer. For example, polyethersulfone can be blended with poly (N-vinylpyrrolidone) and the two polymers can be co-precipitated from solution to form a membrane. However, excess poly (N-vinylpyrrolidone) must be washed away from the membrane with water, which in turn results in wasted valuable material and removes excess poly (N-vinylpyrrolidone). This produces an aqueous effluent containing. Furthermore, the hydrophilic polymer can be filtered out of the membrane during membrane treatment of the aqueous stream. There remains a need for polymers that provide a hydrophilic surface to porous asymmetric membranes made from hydrophobic polymers. The polymer should be hydrophilic and have an affinity for hydrophobic polymers so that it is not extracted by washing during fabrication or during use of the membrane in the final application. .

  The amphiphilic block copolymer comprises a hydrophobic block comprising, consisting essentially of, or consisting of a poly (phenylene ether) block or poly (phenylene ether) copolymer block; and a hydrophilic block or graft; Become or consist of.

  A method for producing an amphiphilic block copolymer comprises a hydrophilic ethylenically unsaturated monomer in the presence of a hydrophobic polymer comprising, consisting essentially of, or consisting of a poly (phenylene ether) or poly (phenylene ether) copolymer To produce an amphiphilic block copolymer.

  The porous asymmetric membrane comprises a hydrophobic polymer comprising, consisting essentially of, or consisting of a poly (phenylene ether) or poly (phenylene ether) copolymer; and a poly (phenylene ether) block or a poly (phenylene ether) copolymer block Comprising, consisting essentially of, or consisting of an amphiphilic block copolymer comprising a hydrophobic block comprising: and a hydrophilic block or graft.

  A method of forming a porous asymmetric membrane includes a hydrophobic polymer comprising, consisting essentially of, or consisting of poly (phenylene ether) or poly (phenylene ether) copolymer, and poly (phenylene ether) or poly (phenylene ether) ) Dissolving an amphiphilic block copolymer comprising a hydrophobic block comprising a copolymer and a hydrophilic block or graft in a water miscible polar aprotic solvent to produce a porous asymmetric membrane-forming composition; Phase-inverting the asymmetric membrane-forming composition in a first non-solvent to form a porous asymmetric membrane; optionally, washing the porous asymmetric membrane in a second non-solvent; and Optionally, drying the porous asymmetric membrane to produce a porous asymmetric membrane.

The scanning electron microscope (SEM) photograph of the surface of Example 6 and the porous asymmetric membrane of 9-10 is shown. It is a diagram of a laboratory scale wet and dry immersion spinning apparatus. 1 shows a laboratory scale hollow fiber membrane module.

  The inventors have found that certain amphiphilic copolymers are particularly useful in the production of asymmetric membranes and hollow fibers used for ultrafiltration. The copolymer comprises a hydrophobic segment that can exist in the form of a block or polymer backbone (poly (phenylene ether) or copolymer thereof); and a hydrophilic segment that can exist in a form grafted to the polymer block or hydrophobic backbone. Have. Amphiphilic copolymers are used with poly (phenylene ether) or copolymers thereof to form flat membranes or hollow fiber membranes.

  Thus, the amphiphilic block copolymer comprises a hydrophobic block and a hydrophilic block or graft, wherein the hydrophobic block comprises a poly (phenylene ether) block or a poly (phenylene ether) copolymer block, then essentially Become or consist of. In some embodiments, the hydrophobic block consists of a poly (phenylene ether) block or a poly (phenylene ether) copolymer block. These amphiphilic block copolymers are random copolymers of hydrophobic ethylenically unsaturated monomers and hydrophilic ethylenically unsaturated monomers, such as random copolymers of styrene and N-vinylpyrrolidone, which are hydrophobic monomer repeat units and hydrophilic A distinction is made in that the monomer repeat units are concentrated in a homopolymer block containing any comonomer. In certain embodiments, the amphiphilic block copolymer comprises 20 to 50 weight percent hydrophobic blocks and 80 to 50 weight percent hydrophilic blocks or grafts. In other embodiments, the amphiphilic block copolymer comprises 50 to 90 weight percent hydrophobic blocks and 50 to 10 weight percent hydrophilic blocks or grafts.

The hydrophobic block of the amphiphilic block copolymer can include poly (phenylene ether). In certain embodiments, the hydrophobic block of the amphiphilic block copolymer comprises the following repeat unit (I):
Poly (phenylene ether) having
Wherein each time Z ¹ appears, it is independently halogen, unsubstituted or substituted C _1-12 hydrocarbyl (provided that the hydrocarbyl group is not a tertiary hydrocarbyl), C _1-12 hydrocarbylthio, C _{1. 12} hydrocarbyloxy or C _{2 to 12} halohydrocarbyloxy (wherein at least two carbon atoms separate the halogen and oxygen atoms), be; Z ² is each appear, independently, hydrogen, halogen, Unsubstituted or substituted C _1-12 hydrocarbyl (provided that the hydrocarbyl group is not a tertiary hydrocarbyl), C _1-12 hydrocarbylthio, C _1-12 hydrocarbyloxy, or C _2-12 halohydrocarbyloxy (where At least two carbon atoms separating the halogen and oxygen atoms) The In certain embodiments, the hydrophobic block comprises poly (2,6-dimethyl-1,4-phenylene ether).

The hydrophobic block of the amphiphilic block copolymer may comprise a poly (phenylene ether) copolymer block, for example a copolymer block comprising units derived from 2,6-dimethylphenol and 2,3,6-trimethylphenol. In certain embodiments, the hydrophobic block of the amphiphilic block copolymer comprises 100 to 20 mole percent of repeating units derived from 2,6-dimethylphenol; and 0 to 80 mole percent of a second monohydric phenol (II A poly (phenylene ether) copolymer block comprising: wherein Z is a C _1-12 alkyl, a C _3-12 cycloalkyl, or a monovalent group (III);
In the monovalent group (III), q is 0 or 1 and R ¹ and R ² are independently hydrogen or C _1-6 alkyl; all mole percentages are the sum of all repeat units The poly (phenylene ether) copolymer block has an intrinsic viscosity of 0.1 to 0.5 deciliters / gram measured in chloroform at 25 ° C.

  The hydrophobic block of the amphiphilic block copolymer can include repeating units derived from 2,6-dimethylphenol. In certain embodiments, the hydrophobic block of the amphiphilic copolymer comprises 80 to 20 mole percent repeat units derived from 2,6-dimethylphenol; and 20 to 80 mole percent derived from a second monohydric phenol. A poly (phenylene ether) copolymer comprising: In certain embodiments, the second monohydric phenol comprises 2-methyl-6-phenylphenol.

  The hydrophilic block or graft of the amphiphilic block copolymer can comprise polymerized hydrophilic ethylenically unsaturated monomers. Ethylenically unsaturated monomers include acrylic esters, methacrylic esters, hydroxyalkyl acrylates, hydroxyalkyl methacrylates, acrylamide derivatives, vinyl pyridine and their alkyl substituted derivatives, vinyl carbazole, vinyl acetate, vinyl sulfonic acid, vinyl phosphoric acid, 4- It can be styrene sulfonic acid, N-vinyl pyrrolidone, or a combination comprising at least one of these. Specific ethylenically unsaturated monomers include acrylic acid, methacrylic acid, ethyl methacrylate, ethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 1-hydroxy-prop-2-yl Acrylate, 2-hydroxyprop-1-yl acrylate, 2,3-dihydroxypropyl acrylate, 2-hydroxyethyl methacrylate, maleic anhydride, acrylamide, N-methylacrylamide, N, N-dimethylacrylamide, vinyl acetate, 2-vinyl Pyridine, 2-methyl-5-vinylpyridine, 2-ethyl-5-vinylpyridine, 2-ethyl-5-vinylpyridine, N-vinylpyrrolidone, N-vinylcarbazole, vinylsulfonic acid, vinyl Phosphoric acid, combinations include phosphoethyl methacrylate, and at least one of these. In some embodiments, the ethylenically unsaturated monomer includes a terminal methoxy-capped poly (ethylene oxide) methacrylate, 4-vinylpyridine, N-vinylpyrrolidone, N, N-dimethylacrylamide, 4-acryloylmorpholine, or Combinations comprising at least one of these are included.

  Amphiphilic block copolymers can be made by polymerization of hydrophilic ethylenically unsaturated monomers in the presence of poly (phenylene ether) or poly (phenylene ether) copolymers, for example, by controlled radical polymerization. In certain embodiments, the polymerization of the hydrophilic ethylenically unsaturated monomer is atom transfer radical polymerization, reversible addition-fragmentation transfer polymerization, or stable free radical polymerization. The polymerization of the hydrophilic ethylenically unsaturated monomer may be graft polymerization. The above description of amphiphilic block copolymers herein also applies to the method for producing amphiphilic block copolymers. For example, in certain embodiments, the hydrophilic ethylenically unsaturated monomer is a terminal methoxylated poly (ethylene oxide) methacrylate, 4-vinylpyridine, vinylpyrrolidone, dimethylacrylamide, 4-acryloylmorpholine, or a combination comprising at least one of these. including.

  The amphiphilic block copolymer comprises a hydrophobic block (which can be referred to as (A)) and a hydrophilic block (which can be referred to as (B)). The sequences of blocks (A) and (B) include linear structures, graft structures, and radial teleblock structures with or without branched chains. Linear block copolymers include tapered linear structures and non-tapered linear structures. In certain embodiments, the hydrophilic block copolymer has a tapered linear structure. In certain embodiments, the hydrophilic block copolymer has a non-tapered linear structure. The structure of the linear block copolymer includes diblock (A-B block), tri-block (A-B-A block, or B-A-B block), tetra-block (A-B-A-B block), And pentablock (ABABABA block or BABABA block) structure, and a total of six or more blocks (A) and (B) in total. A chain structure is included, wherein the molecular weight of each (A) block may be the same as or different from that of the other (A) blocks, and the molecular weight of each (B) block is the other ( B) It may be the same as or different from that of the block. In certain embodiments, the amphiphilic block copolymer is a diblock copolymer. The amphiphilic block copolymer may be a comb-type or brush-type graft copolymer.

  Amphiphilic block copolymers can be used to fabricate porous asymmetric membranes for the production of aqueous streams. In certain embodiments, the porous asymmetric membrane is a hydrophobic polymer comprising a poly (phenylene ether) or poly (phenylene ether) copolymer; and the hydrophobic block is a poly (phenylene ether) block or a poly (phenylene ether) copolymer block And an amphiphilic block copolymer comprising a hydrophilic block or a hydrophilic block or graft.

The hydrophobic polymer may comprise a poly (phenylene ether) having a repeating unit having the structure (I), where each time Z ¹ appears, it is independently halogen, unsubstituted or substituted C _1-12 hydrocarbyl. (Provided that the hydrocarbyl group is not a tertiary hydrocarbyl), C _1-12 hydrocarbylthio, C _1-12 hydrocarbyloxy, or C _2-12 halohydrocarbyloxy, wherein at least two carbon atoms are Each time Z ² appears, it is independently hydrogen, halogen, unsubstituted or substituted C _1-12 hydrocarbyl (provided that the hydrocarbyl group is not a tertiary hydrocarbyl). C _1-12 hydrocarbylthio, C _1-12 hydrocarbyloxy, or C _2-12 Lohydrocarbyloxy, where at least two carbon atoms separate the halogen and oxygen atoms. In certain embodiments, the poly (phenylene ether) comprises poly (2,6-dimethyl-1,4-phenylene ether).

The hydrophobic polymer comprises a poly (100) repeating unit derived from 100 to 20 mole percent 2,6-dimethylphenol; and a repeating unit derived from 0 to 80 mole percent of the second monohydric phenol (II). Phenylene ether) copolymer block, wherein Z is C _1-12 alkyl, C _3-12 cycloalkyl, or a monovalent group (III), and in the monovalent group (III): q is 0 or 1, R ¹ and R ² are independently hydrogen or C _1-6 alkyl; all mole percentages are relative to the total number of moles of all repeat units; The (phenylene ether) copolymer has an intrinsic viscosity of 0.7 to 1.5 deciliters / gram, measured in chloroform at 25 ° C. In certain embodiments, the hydrophobic polymer comprises 80 to 20 mole percent repeat units derived from 2,6-dimethylphenol; and 20 to 80 mole percent repeat units derived from a second monohydric phenol. Includes poly (phenylene ether) copolymers. In certain embodiments, the second monohydric phenol comprises 2-methyl-6-phenylphenol.

  Hydrophobic polymers are 0.7, 0.8, 0.9, 1.0, or 1.1 deciliter / gram or more, 1.5, 1.4, or It may be a poly (phenylene ether) copolymer having an intrinsic viscosity of 1.3 deciliter / gram or less. In certain embodiments, the intrinsic viscosity is 1.1 to 1.3 deciliters / gram.

  In certain embodiments, the poly (phenylene ether) copolymer has a weight average molecular weight of 100,000 to 500,000 daltons (Da) as measured by gel permeation chromatography against a polystyrene standard. Within this range, the weight average molecular weight may be 150,000 or 200,000 Da or more and 400,000, 350,000, or 300,000 Da or less. In an embodiment, the weight average molecular weight is 100,000 to 400,000 Da, in particular 200,000 to 300,000 Da. The poly (phenylene ether) copolymer may have a polydispersity (ratio of weight average molecular weight to number average molecular weight) of 3 to 12. Within this range, the polydispersity can be 4 or 5 or more, 10, 9, or 8 or less.

  The solubility of the hydrophobic polymer in the water miscible polar aprotic solvent is 50 to 400 grams per kilogram based on the combined weight of the hydrophobic polymer and solvent at 25 ° C. Within this range, the solubility at 25 ° C. may be 100, 120, 140, or 160 grams / kilogram or more and 300, 250, 200, or 180 g / kg or less. Advantageously, a hydrophobic polymer having an intrinsic viscosity of 0.7 to 1.5 deciliters / gram, in particular 1.1 to 1.3 deciliters / gram, and a solubility of 50 to 400 grams / kilogram at 25 ° C. Use of results in a film-forming composition having a solution concentration and viscosity that provides good control over the phase-change step of film formation.

  Amphiphilic block copolymers can be 20 to 50 weight percent hydrophobic block and 80 to 50 weight percent hydrophilic block or graft, or 50 to 90 weight percent hydrophobic block and 50 to 10 weight percent hydrophilic. May contain sex blocks or grafts. The hydrophilic block or graft of the amphiphilic block copolymer can comprise polymerized hydrophilic ethylenically unsaturated monomers. Hydrophilic ethylenically unsaturated monomers include acrylic esters, methacrylic esters, hydroxyalkyl acrylates, hydroxyalkyl methacrylates, acrylamide derivatives, vinyl pyridines and their alkyl substituted derivatives, vinyl carbazole, vinyl acetate, vinyl sulfonic acid, vinyl phosphoric acid, It can be 4-styrene sulfonic acid, N-vinyl pyrrolidone, or a combination comprising at least one of these. Specific hydrophilic ethylenically unsaturated monomers include acrylic acid, methacrylic acid, ethyl methacrylate, ethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 1-hydroxy-prop-2 -Yl acrylate, 2-hydroxyprop-1-yl acrylate, 2,3-dihydroxypropyl acrylate, 2-hydroxyethyl methacrylate, maleic anhydride, acrylamide, N-methylacrylamide, N, N-dimethylacrylamide, vinyl acetate, 2 -Vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, 2-ethyl-5-vinylpyridine, 2-ethyl-5-vinylpyridine, N-vinylpyrrolidone, N-vinylcarbazol , Oxazoline, vinyl sulfonic acid, combinations include vinyl phosphoric acid, phosphoethyl methacrylate, and at least one of these. In certain embodiments, the hydrophilic ethylenically unsaturated monomer includes terminal methoxylated poly (ethylene oxide) methacrylate, 4-vinylpyridine, N-vinylpyrrolidone, N, N-dimethylacrylamide, 4-acryloylmorpholine, or at least of these. Combinations containing one are included. In certain embodiments, the hydrophilic block of the amphiphilic block copolymer comprises poly (acrylic acid).

In certain embodiments, the hydrophilic block of the amphiphilic block copolymer used in the porous asymmetric membrane comprises a poly (alkylene oxide) block. The poly (alkylene oxide) block may comprise a poly (alkylene oxide) or poly (alkylene oxide) copolymer, wherein the alkylene oxide monomer is ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, styrene Oxides, or combinations comprising at least one of these. In certain embodiments, the poly (alkylene oxide) comprises poly (ethylene oxide) or a copolymer of ethylene oxide and 1,2-propylene oxide, 1,2-butylene oxide, styrene oxide, or combinations thereof, wherein The poly (alkylene oxide) copolymer contains enough ethylene oxide repeat units for the amphiphilic block copolymer to be hydrophilic. In certain embodiments, the poly (alkylene oxide) block comprises poly (ethylene oxide) repeat units of the formula:
In the formula, n is 1 to 100. The poly (alkylene oxide) copolymer is a block copolymer or random copolymer, monohydroxyl or dihydroxy of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, styrene oxide, or a combination comprising at least one of these. Can be prepared by polyaddition to the initiator compound. The poly (alkylene oxide) may have a number average molecular weight of 200 to 5,000 grams / mole, especially 500 to 2,500 grams / mole.

  In certain embodiments, the hydrophilic block of the amphiphilic block copolymer used in the porous asymmetric membrane comprises poly (ethylene oxide). This hydrophobic block has a number average molecular weight of 10,000 to 100,000 Daltons (Da), in particular about 30,000 Da, and the poly (ethylene oxide) block has a number of 500 to 10,000 Da, in particular about 1,000 Da. Number average molecular weight.

  In certain embodiments, the hydrophilic polymer is excluded from the porous asymmetric membrane. Excluded hydrophilic polymers include, for example, polyacrylamide, poly (N, N-dimethylacrylamide), poly (vinyl alcohol), poly (vinyl ether), poly (vinyl ester), such as poly (vinyl acetate) or poly ( Vinyl propionate), poly (vinyl aldehyde) such as poly (vinyl formal) or poly (vinyl butyral), poly (vinyl amine) such as poly (4-vinyl pyridine), poly (N-vinyl pyrrolidone), poly (N- Vinylimidazole), poly (4-acryloylmorpholine), poly (oxazoline), poly (ethyleneamine), poly (ethylene oxide), poly (propylene oxide), poly (ethylene oxide) monoether, poly (ethylene oxide) and poly (propylene oxide) )of Lock copolymers, poly (terminal alkoxy poly (ethylene oxide) methacrylate), or a combination comprising at least one of these. In certain embodiments, the excluded hydrophilic polymers include poly (N-vinylpyrrolidone), poly (oxazoline), poly (ethylene oxide), poly (propylene oxide), poly (ethylene oxide) monoether or monoester, poly ( Propylene oxide) monoethers or monoesters, poly (ethylene oxide) and poly (propylene oxide) block copolymers, polysorbates, cellulose acetate, or combinations comprising at least one of these. In certain embodiments, the excluded hydrophilic copolymer includes poly (N-vinylpyrrolidone). Hydrophilic polymers have been used in film-forming compositions to impart viscosity to film-forming compositions that help to form porous asymmetric membranes useful for aqueous stream purification. However, hydrophilic polymers, when present in a porous asymmetric membrane, tend to be extracted during the phase inversion and washing steps of membrane fabrication. Further, the hydrophilic polymer can be filtered out of the membrane in end-use application-aqueous flow membrane treatment. For example, polyethersulfone can be blended with poly (N-vinylpyrrolidone) and the two polymers can be co-precipitated from solution to form a membrane. Excess poly (N-vinyl pyrrolidone) must be washed away from the membrane with water, which is consequently a waste of valuable material and an aqueous solution containing excess poly (N-vinyl pyrrolidone). Generate waste liquid. Advantageously, the porous asymmetric membrane described herein is useful for the purification of aqueous streams without a hydrophilic copolymer or any other viscosity modifier.

  The porous asymmetric membrane can be made from poly (2,6-dimethyl-1,4-phenylene ether), polyethersulfone (PESU), polysulfone (PSU), or polyphenylsulfone (PPSU). Advantageously, these polymers are compatible with the hydrophobic polymers described herein. Thus, in addition to the hydrophobic polymers described herein, the porous asymmetric membrane is poly (2,6-dimethyl-1,4-phenylene ether), polyethersulfone, polysulfone, polyphenylsulfone, or A combination including at least one of these may further be included. Thus, a beneficial combination of properties resulting from each hydrophobic polymer in the blend can be obtained.

  The porous asymmetric membrane described herein has many advantageous properties. The amphiphilic block copolymers described herein provide porous asymmetric membranes that have a hydrophilic surface when evaluated, for example, by contact angle. Because of the hydrophilic surface, porous asymmetric membranes can be used for aqueous stream purification and are resistant to fouling. Advantageously, the presence of the amphiphilic block copolymer in the porous asymmetric membrane does not adversely affect the pore size distribution, membrane selectivity, or permeation flux. The poly (phenylene ether) and poly (phenylene ether) copolymers described herein are miscible with the poly (phenylene ether) or poly (phenylene ether) copolymer block of the amphiphilic block copolymer. Thus, the hydrophobic block of the amphiphilic block copolymer tends to dissolve in the poly (phenylene ether) or poly (phenylene ether) copolymer of the porous asymmetric membrane, as indicated by a decrease in the glass transition temperature of the hydrophobic polymer phase. There is. Thus, the amphiphilic block copolymer prevents water extraction. Advantageously, this results in reduced loss of the amphiphilic block copolymer in the phase conversion to membrane and washing steps, and the amphiphilic block copolymer in contact with an aqueous stream in end use applications. Reduce loss.

  The porous asymmetric membrane described herein can be fabricated from a porous asymmetric membrane-forming composition. The porous asymmetric membrane-forming composition is a hydrophobic polymer comprising poly (phenylene ether) or poly (phenylene ether) copolymer; an amphiphilic block copolymer comprising a hydrophobic block and a hydrophilic block or graft, The block comprises an amphiphilic block copolymer comprising a poly (phenylene ether) block or a poly (phenylene ether) copolymer block; and a water miscible polar aprotic solvent; wherein the hydrophobic polymer and amphiphilic The block copolymer is dissolved in a water miscible polar aprotic solvent. The above description of porous asymmetric membranes herein is also applicable to film-forming compositions. For example, in the film-forming composition, the second monohydric phenol of the poly (phenylene ether) copolymer can comprise 2-methyl-6-phenylphenol.

  The porous asymmetric membrane described herein can be prepared from a porous asymmetric membrane-forming composition. Thus, a method for forming a porous asymmetric membrane comprises dissolving a hydrophobic polymer and an amphiphilic block copolymer in a water miscible polar aprotic solvent to produce a porous asymmetric membrane-forming composition, wherein The hydrophobic polymer comprises a poly (phenylene ether) or poly (phenylene ether) copolymer, the amphiphilic block copolymer comprises a hydrophobic block and a hydrophilic block or graft, and the hydrophobic block comprises poly (phenylene ether) Comprising a block or poly (phenylene ether) copolymer block; phase-converting the film-forming composition in a first non-solvent to form a porous asymmetric membrane; Washing in a non-solvent; and drying the porous asymmetric membrane.

  Examples of the water-miscible polar aprotic solvent include N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), N-methyl-2-pyrrolidone (NMP), and N-ethyl-2-pyrrolidone. , Dimethyl sulfoxide (DMSO), dimethyl sulfone, sulfolane, butyrolactone; and combinations comprising at least one of these. In certain embodiments, the water miscible polar aprotic solvent comprises N-methyl-2-pyrrolidone. A solvent mixture comprising a water miscible polar aprotic solvent can be used. The solvent mixture can include water. For example, the solvent mixture can include N-methyl-2-pyrrolidone and water. The solubility of the poly (phenylene ether) copolymer in a water miscible polar aprotic solvent can be from 50 to 400 grams per kilogram based on the combined weight of the poly (phenylene ether) copolymer and the solvent at 25 ° C. Within this range, the solubility at 25 ° C. may be 100, 120, 140, or 160 grams / kilogram or more and 300, 250, 200, or 180 g / kg or less. Advantageously, a hydrophobic polymer solubility of 50 to 400 grams / kilogram provides a film-forming composition that aids in the formation of a porous asymmetric film.

  The first non-solvent composition comprises water, a water miscible polar aprotic solvent, or a combination comprising at least one of these. The water miscible polar aprotic solvent can be any of the water miscible polar aprotic solvents used in the film-forming composition. In certain embodiments, the first non-solvent composition is 10 to 100 weight percent water, and 0 to 90 weight percent N-methyl-2-pyrrolidone, based on the total weight of the first non-solvent composition. including. Within this range, the first non-solvent composition comprises 10 to 90 weight percent, especially 10 to 80 weight percent water, and 10 to 90 weight percent, particularly 20 to 90 weight percent N-methyl-2-pyrrolidone. Can be included. In certain embodiments, the first non-solvent composition comprises about 70 weight percent water and about 30 weight percent N-methyl-2-pyrrolidone. The first non-solvent composition serves as a condensation or phase change bath for the film-forming composition. The film is formed by contacting the film-forming composition with the first non-solvent composition. In the film-forming composition, the copolymer is near its gel point and sets or precipitates as a film or hollow fiber.

  The first non-solvent serves as a condensation or phase change bath for the porous asymmetric film-forming composition. The film is formed by contacting the film-forming composition with a first non-solvent. The hydrophobic polymer can be near its gel point in the film-forming composition, but sets or precipitates as a film or hollow fiber. The second non-solvent serves to optionally wash away the remaining water-miscible solvent and, if present, the hydrophilic polymer from the membrane. The first and second non-solvents can be the same or different and can comprise water or a mixture of water and a water miscible polar aprotic solvent. In certain embodiments, the first and second non-solvents are independently water or a mixture of water / N-methyl-2-pyrrolidone. In certain embodiments, the first and second non-solvent are both water. Water can be deionized.

  Any of several techniques for the film formation phase change step can be used. For example, the phase inversion step may be a dry phase separation method in which the dissolved hydrophobic polymer is precipitated by evaporation of a sufficient amount of solvent mixture to form a membrane. The phase inversion step may also be a wet phase separation method, in which the dissolved hydrophobic polymer is deposited by immersion in a first non-solvent to form a membrane. The phase inversion step may be a dry-wet phase separation process, which is a combination of dry and wet phase processes. The phase inversion step may be a thermally induced separation method, in which the dissolved hydrophobic polymer precipitates or condenses with controlled cooling to form a membrane. Once formed, the membrane can undergo conditioning or pretreatment of the membrane prior to its end use. Conditioning or pretreatment can be thermal annealing to relieve stress, or pre-equilibration in the expected aqueous feed. The above description of a porous asymmetric membrane herein is also applicable to a method of forming a porous asymmetric membrane. For example, in the method of forming a porous asymmetric membrane, the second monohydric phenol of the poly (phenylene ether) copolymer can comprise 2-methyl-6-phenylphenol.

  The molecular weight cut-off (MWCO) of a membrane is the lowest molecular weight solute in which more than 90 weight percent (wt%) of the solute is retained by the membrane. Porous asymmetric membranes produced by the above method are 500 to 40,000 daltons (Da), in particular 1,000 to 20,000 Da, more particularly 2,000 to 8,000 Da, and even more particularly , 3,000 to 7,000 Da MWCO. Furthermore, any of the above MWCO ranges can be present in combination with a desired permeate flux, eg, a clean water permeate flux (CWF). Flux across the membrane is driven by osmosis across the membrane, or absolute pressure differential, referred to herein as trans-membrane pressure (TMP). The transmembrane pressure can be from 1 to 500 kilopascals (kPa), in particular from 2 to 400 kPa, more particularly from 4 to 300 kPa.

  The porous asymmetric membrane can be in the form of a porous asymmetric hollow fiber. The diameter of the yarn can be 50 to 5000 micrometers (μm), in particular 100 to 2000 μm. The porous asymmetric hollow fiber module may include a bundle of porous asymmetric hollow fibers. In certain embodiments, the bundle of yarns includes 10 to 10,000 porous asymmetric hollow fibers. The asymmetric hollow fiber can be bundled in the longitudinal direction, potted with a curable resin at both ends, and housed in a pressure vessel to form an asymmetric hollow fiber module.

  Depending on the pore size, the porous asymmetric membrane described herein can be used for media filtration, microfiltration, ultrafiltration, nanofiltration, or reverse osmosis. For media filtration, the pore size can be from about 100 to about 1,000 micrometers. For microfiltration, the pore size can be from about 0.03 to about 10 micrometers. For ultrafiltration, the pore size can be from about 0.002 to about 0.1 micrometers. For nanofiltration, the pore size can be from about 0.001 to about 0.002 micrometers. In certain embodiments, the porous asymmetric membrane has a surface pore size of 0.001 to 0.05 micrometers (μm), in particular 0.005 to 0.01 μm. For reverse osmosis, the pore size can be about 0.0001 to 0.001 micrometers. The module can also be a membrane contactor module, a pervaporation module, a dialysis module, an osmosis module, an electrodialysis module, a membrane electrolysis module, an electrophoresis module, and a membrane distillation module.

  The porous asymmetric membrane disclosed herein is useful for the treatment of aqueous streams. Depending on the pore size and morphology of the porous asymmetric membrane, the membrane can be suspended, particulate, sand, silt, clay, cyst, algae, microorganisms, bacteria, viruses, colloids, synthetic and natural It can be used to remove industrial macromolecules, dissolved organic compounds, salts, or combinations comprising at least one of these. Thus, the porous asymmetric membranes disclosed herein can be used in wastewater treatment, water purification, food processing, dairy, biotechnology, pharmaceuticals, and healthcare.

  Embodiment 1. FIG. A hydrophobic block comprising, consisting essentially of or consisting of a poly (phenylene ether) block or poly (phenylene ether) copolymer block; and comprising, consisting essentially of or consisting of a hydrophilic block or graft; Amphiphilic block copolymer.

  Embodiment 2. An amphiphilic block copolymer of Embodiment 1 comprising from 50 to 50 weight percent hydrophobic block and from 50 to 80 weight percent hydrophilic block or graft.

Embodiment 3. FIG. The hydrophobic block comprises a poly (phenylene ether) having a repeating unit (I), where each time Z ¹ appears, it is independently halogen, unsubstituted or substituted C _1-12 hydrocarbyl, provided that the hydrocarbyl group is Not a tertiary hydrocarbyl), C _1-12 hydrocarbylthio, C _1-12 hydrocarbyloxy, or C _2-12 halohydrocarbyloxy (wherein at least 2 carbon atoms separate the halogen and oxygen atoms) Each time Z ² appears, it is independently hydrogen, halogen, unsubstituted or substituted C _1-12 hydrocarbyl (provided that the hydrocarbyl group is not a tertiary hydrocarbyl), C _1-12 hydrocarbylthio. , C _1-12 hydrocarbyloxy, or C _2-12 halohydrocarbyloxy ( Wherein at least two carbon atoms separate the halogen and oxygen atoms; the amphiphilic block copolymer of embodiment 1 or 2.

Embodiment 4 FIG. A poly (hydrophobic block comprising 100 to 20 mole percent repeat units derived from 2,6-dimethylphenol; and 0 to 80 mole percent repeat units derived from a second monohydric phenol (II). Phenylene ether) copolymers, wherein Z is C _1-12 alkyl or cycloalkyl, or a monovalent group (III), where q is 0 or 1, R ¹ and R ² _Are independently hydrogen or C _1-6 alkyl; all mole percentages are relative to the total moles of all repeating units; poly (phenylene ether) copolymer block measured in chloroform at 25 ° C. Having an intrinsic viscosity of 0.1 to 0.5 deciliters / gram; the amphiphilic block copolymer of any one of embodiments 1-3 polymer.

  Embodiment 5. FIG. 80 to 20 mole percent repeat units derived from 2,6-dimethylphenol, and 20 to 80 mole percent repeat units derived from a second monohydric phenol (II), wherein the hydrophobic block of the amphiphilic copolymer is The amphiphilic block copolymer of any one of embodiments 1-4, comprising a poly (phenylene ether) copolymer comprising:

  Embodiment 6. FIG. The amphiphilic block copolymer of embodiment 5, wherein the second monohydric phenol comprises 2-methyl-6-phenylphenol.

  Embodiment 7. FIG. The amphiphilic block copolymer of embodiments 1-6, wherein the hydrophobic block or graft comprises polymerized hydrophilic ethylenically unsaturated monomers.

  Embodiment 8. FIG. A combination in which the hydrophilic ethylenically unsaturated monomer comprises terminal methoxylated poly (ethylene oxide) methacrylate, 4-vinylpyridine, N-vinylpyrrolidone, N, N-dimethylacrylamide, 4-acryloylmorpholine, or at least one of these The amphiphilic block copolymer of embodiment 7, comprising:

  Embodiment 9. FIG. Polymerization of hydrophilic ethylenically unsaturated monomers in the presence of hydrophobic polymers comprising, consisting essentially of, or consisting of poly (phenylene ether) or poly (phenylene ether) copolymers to produce amphiphilic block copolymers A process for producing an amphiphilic block copolymer.

  Embodiment 10 FIG. Embodiment 10. The method of Embodiment 9 wherein the polymerization is controlled radical polymerization.

  Embodiment 11. FIG. Embodiment 11. The method of Embodiment 10 wherein the controlled radical polymerization is atom transfer radical polymerization, reversible addition cleavage transfer polymerization, or stable free radical polymerization.

  Embodiment 12 FIG. Embodiment 10. The method of Embodiment 9 wherein the polymerization is graft polymerization.

  Embodiment 13 FIG. The hydrophilic ethylenically unsaturated monomer comprises a terminal methoxylated poly (ethylene oxide) methacrylate, 4-vinylpyridine, vinylpyrrolidone, N, N-dimethylacrylamide, 4-acryloylmorpholine, or a combination comprising at least one of these, The method of any of Embodiments 9-12.

  Embodiment 14 FIG. A hydrophobic polymer comprising, consisting essentially of or consisting of a poly (phenylene ether) or poly (phenylene ether) copolymer; and a hydrophobic block comprising a poly (phenylene ether) block or a poly (phenylene ether) copolymer block; A porous asymmetric membrane comprising, consisting essentially of or consisting of an amphiphilic block copolymer comprising a hydrophilic block or graft.

  Embodiment 15. FIG. Hydrophobic polymers comprising, consisting essentially of or consisting of poly (phenylene ether) or poly (phenylene ether) copolymers; hydrophobic blocks and hydrophilicity comprising poly (phenylene ether) blocks or poly (phenylene ether) copolymer blocks An amphiphilic block copolymer comprising a block or graft; and a water miscible polar aprotic solvent; comprising, consisting essentially of, or consisting of a hydrophobic polymer and an amphiphilic block copolymer that are water miscible A porous asymmetric membrane-forming composition dissolved in a polar aprotic solvent.

  Embodiment 16. FIG. A method of forming a porous asymmetric membrane comprising a hydrophobic polymer comprising, consisting essentially of or consisting of poly (phenylene ether) or poly (phenylene ether) copolymer, and poly (phenylene ether) or poly ( Dissolving an amphiphilic block copolymer comprising a hydrophobic block comprising a (phenylene ether) copolymer and a hydrophilic block or graft in a water miscible polar aprotic solvent to produce a porous asymmetric membrane-forming composition; Phase-transforming the porous asymmetric membrane-forming composition in a first non-solvent to form a porous asymmetric membrane; optionally, washing the porous asymmetric membrane in a second non-solvent; And optionally drying the porous asymmetric membrane to produce a porous asymmetric membrane.

Embodiment 17. FIG. The hydrophobic polymer comprises a poly (phenylene ether) having repeating units (I), wherein each time Z ¹ appears, it is independently halogen, unsubstituted or substituted C _1-12 hydrocarbyl (provided that the hydrocarbyl group) Is not a tertiary hydrocarbyl), C _1-12 hydrocarbylthio, C _1-12 hydrocarbyloxy, or C _2-12 halohydrocarbyloxy, where at least two carbon atoms separate the halogen and oxygen atoms And)
Each time Z ² appears, it is independently hydrogen, halogen, unsubstituted or substituted C _1-12 hydrocarbyl (provided that the hydrocarbyl group is not a tertiary hydrocarbyl), C _1-12 hydrocarbylthio, C _1- Embodiment _12. The porous asymmetric membrane of any of embodiments 14-16, wherein the composition is ₁₂ hydrocarbyloxy, or C _2-12 halohydrocarbyloxy, wherein at least 2 carbon atoms separate the halogen and oxygen atoms. Thing or method. Embodiment 18. FIG. A poly () wherein the hydrophobic polymer comprises 100 to 20 mole percent repeat units derived from 2,6-dimethylphenol; and 0 to 80 mole percent repeat units derived from a second monohydric phenol (II). Phenylene ether) copolymers, wherein Z is C _1-12 alkyl or cycloalkyl, or the monovalent group (III);
Where q is 0 or 1, R ¹ and R ² are independently hydrogen or C _1-6 alkyl; the mole percent is relative to the total number of moles of all repeating units; The (phenylene ether) copolymer has an intrinsic viscosity of 0.7 to 1.5 deciliters per gram measured in chloroform at 25 ° C.
Embodiment 18. A porous asymmetric membrane, composition, or method of any of embodiments 14-17.

  Embodiment 19. FIG. A poly (phenylene ether) wherein the hydrophobic polymer comprises 80 to 20 mole percent repeat units derived from 2,6-dimethylphenol; and 20 to 80 mole percent repeat units derived from a second monohydric phenol. The porous asymmetric membrane, composition, or method of any of embodiments 14-18, comprising a copolymer.

  Embodiment 20. FIG. Embodiment 21. The porous asymmetric membrane, composition, or method of Embodiment 19 wherein the second monohydric phenol comprises 2-methyl-6-phenylphenol.

  Embodiment 21. FIG. The porous asymmetric membrane, composition, or method of any of embodiments 14-20, wherein the hydrophobic polymer has an intrinsic viscosity of 0.7 to 1.5 deciliters per gram, as measured in chloroform at 25 ° C. .

  Embodiment 22. FIG. Embodiment 14-14 wherein the solubility of the hydrophobic polymer in the water miscible polar aprotic solvent is 50 to 400 grams per kilogram based on the combined weight of the poly (phenylene ether) copolymer and the solvent at 25 ° C. 21. Any of the 21 porous asymmetric membranes, compositions or methods.

  Embodiment 23. FIG. The porous asymmetric membrane, composition, or any of embodiments 14-22, wherein the amphiphilic block copolymer comprises 20 to 50 weight percent hydrophobic block and 50 to 80 weight percent hydrophilic block or graft Method.

  Embodiment 24. FIG. Embodiment 24. The porous asymmetric membrane, composition, or method of any of embodiments 14-23, wherein the hydrophobic block of the amphiphilic block copolymer comprises a poly (phenylene ether) copolymer.

Embodiment 25. FIG. The hydrophobic block of the amphiphilic block copolymer comprises a poly (phenylene ether) block having repeating units (I), wherein each time Z ¹ appears, it is independently halogen, unsubstituted or substituted C _1-12. Hydrocarbyl (provided that the hydrocarbyl group is not a tertiary hydrocarbyl), C _1-12 hydrocarbylthio, C _1-12 hydrocarbyloxy, or C _2-12 halohydrocarbyloxy, wherein at least 2 carbon atoms Each time Z ² appears, independently, hydrogen, halogen, unsubstituted or substituted C _1-12 hydrocarbyl (provided that the hydrocarbyl group is not a tertiary hydrocarbyl). _{), C 1 to 12 hydrocarbylthio, C 1 to 12} hydrocarbyloxy, also (Wherein at least two carbon atoms separate the halogen and oxygen atoms) C _{2 to 12} halohydrocarbyloxy is; either porous asymmetric membrane embodiments 14 to 24, the composition or method.
Embodiment 26. FIG. The hydrophobic block of the amphiphilic block copolymer has 100 to 20 mole percent repeat units derived from 2,6-dimethylphenol; and 0 to 80 mole percent repeats derived from the second monohydric phenol (II) A poly (phenylene ether) copolymer block comprising: wherein Z is C _1-12 alkyl or cycloalkyl, or a monovalent group (III), wherein q is 0 or 1 R ¹ and R ² are independently hydrogen or C _1-6 alkyl; all mole percentages are relative to the total number of moles of all repeat units; the poly (phenylene ether) copolymer block is Poly (phenyle) having an intrinsic viscosity of 0.1 to 0.5 deciliter / gram measured in chloroform at 25 ° C. The porous asymmetric membrane, composition, or method of any of embodiments 14-25.

  Embodiment 27. FIG. The hydrophobic block of the amphiphilic block copolymer is 80 to 20 mole percent repeat units derived from 2,6-dimethylphenol; and 20 to 80 mole percent repeat units derived from a second monohydric phenol; Embodiment 25. The porous asymmetric membrane of embodiment 24 comprising a poly (phenylene ether) copolymer block comprising.

  Embodiment 28. FIG. The porous asymmetric membrane, composition, or method of any of embodiments 18-20, or 27-28, wherein the second monohydric phenol is 2-methyl-6-phenylphenol.

  Embodiment 29. FIG. 29. The porous asymmetric membrane, composition, or method of any of embodiments 14-28, wherein the hydrophilic block or graft of the amphiphilic block copolymer comprises polymerized hydrophilic ethylenically unsaturated monomer.

  Embodiment 30. FIG. A combination in which the hydrophilic ethylenically unsaturated monomer comprises terminal methoxylated poly (ethylene oxide) methacrylate, 4-vinylpyridine, N-vinylpyrrolidone, N, N-dimethylacrylamide, 4-acryloylmorpholine, or at least one of these 30. The porous asymmetric membrane, composition, or method of any of embodiments 14-29.

  Embodiment 31. FIG. Embodiments 14-30, wherein the hydrophilic block comprises poly (ethylene oxide) or a copolymer of ethylene oxide and 1,2-propylene oxide, 1,2-butylene oxide, styrene oxide, or a combination comprising at least one of these. Any of the porous asymmetric membranes, compositions, or methods.

  Embodiment 32. FIG. 32. The porous asymmetric membrane, composition, or method of any of embodiments 14-31, wherein the hydrophilic block of the amphiphilic block copolymer comprises poly (ethylene oxide).

  Embodiment 33. FIG. The porous asymmetric membrane, composition, or method of any of embodiments 14-32, wherein a hydrophilic polymer is excluded.

  Embodiment 34. FIG. The hydrophilic polymer is poly (N-vinylpyrrolidone), poly (oxazoline), poly (ethylene oxide), poly (propylene oxide), poly (ethylene oxide) monoether or monoester, poly (propylene oxide) monoether or monoester, 34. The porous asymmetric membrane, composition, or method of any of embodiments 33, which is a block copolymer of poly (ethylene oxide) and poly (propylene oxide), polysorbate, cellulose acetate, or a combination comprising at least one of these.

  Embodiment 35. FIG. The porous of any of embodiments 14-34, further comprising poly (2,6-dimethyl-1,4-phenylene ether), polyethersulfone, polysulfone, polyphenylsulfone, or a combination comprising at least one of these. An asymmetric membrane, composition, or method.

  Embodiment 36. FIG. 36. The porous asymmetric membrane according to any of embodiments 17-35, wherein the form of the porous asymmetric membrane is a sheet, disk, spiral wound, plate & frame, hollow fiber, capillary, and tubular.

  Embodiment 37. FIG. 36. The porous asymmetric membrane of any of embodiments 17-35, wherein the membrane is a porous asymmetric flat sheet.

  Embodiment 38. FIG. 36. The porous asymmetric membrane of any of embodiments 17-35, wherein the asymmetric membrane is in the form of a spiral.

  Embodiment 39. FIG. The porous asymmetric membrane of any of embodiments 17-35, wherein the membrane is a porous asymmetric hollow fiber.

  Embodiment 40. FIG. 40. A separation module comprising the porous asymmetric membrane of any of embodiments 17-39.

  Embodiment 41. FIG. 41. The separation module of embodiment 40, wherein the separation module is designed for dead-end filtration, external pressure filtration, internal pressure filtration, or crossflow filtration.

  Embodiment 42. FIG. 41. The separation module of embodiment 40, wherein the separation module is a microfiltration module, a nanofiltration module, an ultrafiltration module, a reverse osmosis module, a water pretreatment module, or a membrane distillation module.

  Embodiment 43. FIG. 41. The separation module of embodiment 40, comprising a bundle of asymmetric hollow fibers.

  Embodiment 44. FIG. 44. The separation module of embodiment 43, wherein the bundle of asymmetric hollow fibers is disposed in an enclosure configured for fluid separation.

  Embodiment 45. FIG. 45. The separation module of any of embodiments 40-44, wherein the enclosure is configured to include a bundle and has an outlet configured to remove permeate fluid; a thermosetting or thermoplastic polymer material A first container that is positioned at the first end of the bundle, wherein the hollow fiber membrane is fitted into the first container and communicated through the first container. A first receptacle arranged to be open at the outer surface of the bundle; comprising a thermosetting or thermoplastic polymer material and located at the second end of the bundle opposite the first end of the bundle A second housing body, wherein the hollow fiber membrane is fitted into the second housing body, communicated through the second housing body, and arranged to be open on the outer surface of the second housing body. Two receptacles; a bundle or at or near the first receptacle A first end cap attached to and configured to seal the first end of the enclosure; attached to the second end of the bundle or enclosure at or near the second receptacle A second end cap arranged to seal; an inlet for introducing a fluid mixture to be separated into the bore of the hollow fiber membrane in the first receptacle; and a retention in the second receptacle A separation module comprising: an outlet for removing fluid from the bore of the hollow fiber membrane.

  Embodiment 46. FIG. The separation module of any of embodiments 40-45, comprising a plurality of bundles.

  Embodiment 47. 43. The separation module of any of embodiments 40-42, comprising a hollow core comprising holes; an asymmetric membrane wound around the core; and a spacer disposed adjacent to the asymmetric membrane.

  Embodiment 48. FIG. 48. The separation module of any of embodiments 40-42 and 47, further comprising at least one of an inner spacer or an outer spacer adjacent to the asymmetric membrane.

  Embodiment 49. 38. A spiral wound module comprising the porous asymmetric flat sheet of embodiment 37.

  Embodiment 50. A hollow fiber module comprising between 10 and 10,000 porous asymmetric hollow fibers of embodiment 39.

  Embodiment 51. FIG. Passing the feed stream through the separation module of any of embodiments 40-50 so that it contacts the first surface of the porous asymmetric membrane and passing the permeate through the porous asymmetric membrane Obtaining a permeate stream and a concentrated feed stream.

  Embodiment 52. FIG. 40. A dialysis device for performing hemodialysis on a patient suffering from liver failure, comprising the porous asymmetric membrane of any of embodiments 17-35 or 36-39.

  Embodiment 53. FIG. Embodiment 52. The dialysis device of embodiment 52, comprising the separation module of any of embodiments 40-48.

  Embodiment 54. FIG. 54. The dialysis device of embodiment 53, wherein the asymmetric membrane passes molecules having a molecular weight of up to 45 kilodaltons with a sieving coefficient of 0.1 to 1.0 in the presence of whole blood; Reducing the concentration of protein-bound toxins and inflammatory cytokines in the blood of the patient; a dialysis device reduces the concentration of unconjugated bilirubin and bile acids in the blood of the patient; dialysis passing through the dialysis membrane A dialysis device wherein the fluid comprises 1% to 25% human serum albumin. A method of dialysis, wherein the blood is passed through the separation module of claim 52 such that the blood contacts the first surface of the porous asymmetric membrane, and the dialysis solution is passed through the separation module. Removing the waste product from the blood by passing through the opposing second surface of the porous asymmetric membrane.

  Embodiment 56. FIG. A method for the treatment of liver failure, comprising performing hemodialysis on a patient suffering from liver failure using a liver dialysis device comprising the porous asymmetric membrane of any of embodiments 17-35 or 36-39. Including methods.

  Embodiment 57. FIG. 56. The method for the treatment of liver failure of embodiment 56, wherein the dialysis device comprises the separation module of any of embodiments 40-50.

  Embodiment 58. FIG. A method for sugar purification, wherein a fluid comprising a combination of polysaccharides is passed through the separation module of any of embodiments 40-50 such that the fluid contacts the first surface of the porous asymmetric membrane; and And purifying the sugar by passing the polysaccharide through the membrane.

  Embodiment 59. 49. Passing a fluid containing protein or enzyme through the separation module of any of claims 40-48 such that the fluid contacts the first surface of the porous asymmetric membrane; and passing the components through the membrane Removing a component thereof from the fluid to obtain a protein or enzyme rich retentate stream and recovering the protein or enzyme.

  Embodiment 60. FIG. Generating purified water through the feed water through any of the separation modules of embodiments 40-50 such that the feed water contacts the first surface of the porous composite membrane at a pressure above the osmotic pressure. Water purification method.

  Embodiment 61. FIG. A concentration module comprising the porous asymmetric membrane of any of embodiments 17-39 for concentrating the feed and diluting the recirculated hypertonic solution to produce a slipstream; and receiving and recirculating the slipstream A water pretreatment system, comprising a water replenishment element for bringing the slipstream together with the hypertonic solution to supply solute to the hypertonic solution, wherein the recirculating hypertonic solution is suitable for desalting

  Embodiment 62. FIG. 64. The water pretreatment system of embodiment 61, wherein the concentrator comprises the separation module of any of embodiments 40-48.

  Embodiment 63. FIG. A method for pretreating water comprising receiving feed water; dividing the feed water into a concentrator feed and a slipstream; in a concentrator comprising the porous asymmetric membrane of embodiments 17-39, the concentrator feed is Treating to produce a hypertonic solution; and combining the slipstream and the hypertonic solution to produce an effluent that can be broken down into purified water and a recirculated hypertonic solution.

  Embodiment 64. FIG. 64. The method of embodiment 63, wherein the concentrator comprises the separation module of any of embodiments 40-50.

  Embodiment 65. FIG. A housing, a plurality of hollow fibers comprising the porous asymmetric membrane of any of embodiments 17-39, disposed in the housing and for transporting a first fluid therethrough, in fluid communication with the yarn and to the first A first inlet for delivering a fluid, a fluid in communication with the yarn, a first outlet for receiving the first fluid therefrom, a fluid in communication with a region located outside the hollow fiber, a second And a second outlet.

  Embodiment 66. FIG. Embodiment 65. The blood oxygenator of embodiment 65 wherein a porous asymmetric membrane is included in the separation module of any of embodiments 40-48.

  Embodiment 67. FIG. Embodiment 66. The blood oxygenator of embodiment 66, wherein the first fluid is blood and the second fluid is an oxygen-containing gas.

  Embodiment 68. FIG. Embodiment 66. The blood oxygenator of embodiment 66, wherein the first fluid is blood and the second fluid is a liquid comprising molecular oxygen.

  Embodiment 69. 40. A separation module for the treatment of oil-containing wastewater, wherein the water-insoluble oil is separated from the oil-containing wastewater and comprises the porous asymmetric membrane of any of embodiments 17-39.

  Embodiment 70. FIG. 70. A system for wastewater treatment comprising the separation module of embodiment 69.

  Embodiment 71. FIG. 71. A method of wastewater treatment comprising treating oil-containing wastewater with the system of embodiment 70.

  Embodiment 72. FIG. 72. The embodiment of embodiment 71, further comprising sending a cleaning liquid containing an aqueous alkaline solution toward the surface of the porous asymmetric membrane to remove water-insoluble oil adhering to the surface of the porous asymmetric membrane of the separation membrane module. Method.

  Embodiment 73. FIG. An ultrafiltration device, configured as a filter housing for a separation module, comprising a filter housing with an inlet and an outlet, and a tubular or capillary porous asymmetric membrane adapted to the filter housing Embodiment 36. The porous asymmetric membrane of embodiment 36, wherein the tubular or capillary membrane is permanently hydrophilic, the tubular or capillary membrane is open at the first inlet end and sealed at the other end Supported by a membrane holder that closes the space between the capillary membrane and the filter housing at the first end, so that the pore size of the tubular or capillary ultrafiltration membrane is in the direction of liquid flow. Decreasing device.

  Embodiment 74. FIG. Liquid purification by membrane distillation comprising: a feed channel; a distillate channel; and a retentate channel; wherein the distillate channel and the retentate are separated by a porous asymmetric membrane of any of embodiments 17-39. Equipment for.

  Embodiment 75. FIG. Embodiment 74. An apparatus for purification of a liquid by membrane distillation according to embodiment 74, the first distribution chamber for the feed liquid being fed, on the opposite side of the first distribution chamber for the feed liquid being discharged A second distribution chamber located, a third distribution chamber for the supplied retentate stream, and a fourth distribution chamber opposite the third distribution chamber for the discharged retentate stream. A first pump for sending a feed stream to the segment under pressure and a second distribution chamber for sending a retentate stream to the retentate channel under pressure The wall between the feed channel and the distillate channel includes a cooler surface in the form of a non-porous membrane, and the wall between the retentate channel and the distillate channel is porous. Asymmetric membrane Wherein, inside the retentate channel, such that the flow of fluid to the heat transfer contact with the retentate stream, additional channels are arranged, device.

  The invention is further illustrated by the following non-limiting examples.

Preparative Example: Synthesis of MPP-DMP Copolymer The preparation, characterization and properties of poly (phenylene ether) are described in G. Cooper and J.C. Bennett, Polymerization Kinetics and Technology, Volume 128, pages 230-257, June 01, 1973 (ACS Advances in Chemistry Series). The MPP-DMP copolymer was prepared by dissolving the monomer in toluene and conducting oxidative copolymerization mediated by a copper-diamine complex catalyst in the presence of oxygen. The copolymerization was carried out in a bubbling polymerization reactor equipped with a stirrer, temperature control system, nitrogen encapsulation, oxygen bubbling tube, and computer control system. The reactor was also equipped with a feed pot and pump for charging the reactants into the reactor. When the desired degree of polymerization was reached, the oxygen flow was stopped and the copper complex was removed from the toluene solution by liquid-liquid extraction with a water-soluble chelating agent. The DMP-MPP copolymer was recovered by non-solvent precipitation by pouring the toluene solution into excess methanol with vigorous stirring and then dried in a 120 ° C. oven under a stream of dry nitrogen.

  The polymers can be evaluated for their glass transition temperature (Tg) using differential scanning calorimetry (DSC). The molecular weight distribution of the polymer can be evaluated by size exclusion chromatography using chloroform as the mobile phase and calibration against polystyrene standards. Alternatively, the degree of polymerization can be evaluated by measuring the intrinsic viscosity (IV) in chloroform using the Ubbelohde method.

Preparative Example 1: Preparation of MPP-DMP copolymer with 50 mole percent MPP in 1.8 liter reactor Toluene (622.88 grams), DBA (8.1097 grams), DMBA (30.71 grams) And 5.44 grams of a diamine mixture consisting of 30 weight percent (wt%) DBEDA, 7.5 weight percent QUAT, and the balance toluene, were charged to the bubbling polymerization reactor at 25 ° C. under a nitrogen atmosphere. Stirring was performed. A mixture of 6.27 grams of HBr and 0.5215 grams of Cu ₂ O was added. The oxygen flow to the vessel began 4 minutes after the addition of the monomer mixture. The reactor temperature was increased to 40 ° C. in 18 minutes, maintained at 40 ° C. for 57 minutes, increased to 45 ° C. in 11 minutes, maintained at 45 ° C. for 33 minutes, and increased to 60 ° C. in 10 minutes. 403.67 grams of monomer solution (20.3 wt% DMP, 30.6 wt% MPP and 49.1 wt% toluene) was added over 35 minutes. The oxygen flow was maintained for 115 minutes, at which point the oxygen flow was stopped and the reaction mixture was immediately transferred to a vessel containing 11.07 grams of NTA salt and 17.65 grams of DI (deionized) water. The resulting mixture was stirred at 60 ° C. for 2 hours and then allowed to phase separate. The decanted light phase was precipitated in methanol, filtered, reslurried in methanol and filtered again. After drying in a vacuum oven under a nitrogen blanket at 110 ° C., the copolymer was obtained as a dry powder.

Preparative Examples 2-4: Preparation of MPP-DMP Copolymers with 20, 50, and 80 mole% MPP and IV of about 1 deciliter / gram The process of Preparative Example 1 is made of 1 gallon steel. Scaled up to a bubbling reactor and copolymerization was carried out as described above. The components of the batch reactor charge and continuous monomer feed solution are shown in Table 2. After charging the reactor, the contents were brought to 25 ° C. with stirring, after which a continuous feed of monomer in toluene and then oxygen feed was started. The monomer / toluene mixture was fed over 45 minutes and the oxygen feed was maintained up to 130 minutes. The reactor temperature was increased to 45 ° C. in 90 minutes and then to 60 ° C. in 130 minutes. The reactor contents are then transferred to a separate container for the addition of NTA to chelate copper, and then the toluene phase is separated from the aqueous phase by centrifugation, and the copolymer solution as described above. It was poured into methanol for precipitation.

The dried copolymer was evaluated for molecular weight distribution by gel permeation chromatography (GPC) using CHCl ₃ as solvent and contrasting to polystyrene standards. Intrinsic viscosity (IV) is measured with a CHCl ₃ solution at 25 ° C. using an Ubbelohde viscometer and expressed in units of deciliter / gram (dL / g). The glass transition temperature Tg is measured using differential scanning calorimetry (DSC) and is expressed in ° C. The results of Examples 1-4 are summarized in Table 3. “Mn” represents a number average molecular weight, “Mw” represents a weight average molecular weight, “D” represents polydispersity, and “g” represents gram.

Examples 5-10: General Procedure for Casting Membranes by Solvent / Non-solvent Phase Inversion In general, porous asymmetric membranes are MPP-DMP copolymers and poly (phenylene ether) blocks or poly (phenylene ether) Dissolving an amphiphilic block copolymer comprising a copolymer block and a hydrophilic block or graft in N-methyl-2-pyrrolidone (NMP), respectively, at a concentration of about 16 wt% and about 1 to 10 wt%; Casting was performed by pouring the viscous casting solution onto the glass plate; and pulling with a casting knife through a thin film 150-250 micrometers thick across the plate. A glass plate with a thin film of MPP-DMP in NMP was placed in the first condensation bath for 10-15 minutes. The first coagulation bath was a mixture of NMP and water that promoted copolymer precipitation and coagulation on the porous asymmetric membrane. The coagulated copolymer film floats away from the glass plate when coagulation is substantially complete, at which point it is transferred to a second bath, where it is immersed in clean water, washed, and residual NMP Was removed.

  The above process is described in more detail as follows. MPP-DMP copolymer and an amphiphilic block copolymer comprising a poly (phenylene ether) block or poly (phenylene ether) copolymer block and a hydrophilic block or graft are combined in a 20 milliliter (mL) glass vial for a total of 8 Dissolved in 10 g of chromatography grade NMP, sealed tightly and placed on a low speed roller for 13-48 hours until a homogeneous solution was obtained. The solution was poured into a slender puddle and moved by hand at a constant speed with a doctor blade of adjustable height. The entire glass plate with the cast copolymer solution was completely submerged in the first non-solvent bath (10-100% DI water in NMP) until the membrane began to peel off the plate. The membrane was removed from the glass plate and transferred to a non-solvent bath in the middle of 100 wt% DI water and the corners were pushed down with the weight of the glass stopper so that the NMP was replaced by the water bath. After 15-45 minutes, the membrane was transferred to a final non-solvent bath of 100 wt% water overnight and completely submerged with weight to allow complete solvent exchange of the pores. The membrane was dried at room temperature. Characterization was performed on a specimen cut from the most uniform part in the middle of the membrane. The viscosity of the NMP solution of the copolymer was measured at 20 ° C. using a Brookfield RDV-IIPro viscometer equipped with a small sample adapter and a cylinder spindle.

Membrane Characterization A simple assessment of water flow through the membrane was performed by cutting a 47 millimeter (mm) circle from the membrane and placing it in a fritted funnel and secured. The vacuum filter flask was weighed to zero with a scale, then 100 g of water was placed in the fritted funnel and a vacuum of 1 atm was applied for 15-60 min (min). All data was normalized to a 60 minute run time. The water flow was calculated by placing the vacuum filter flask on a zero adjusted scale and recording the value.

  The surface porosity and cross-sectional morphology of the membrane was evaluated using a Carl Zeiss Supra VP scanning electron microscope (SEM). The “top” membrane surface (initially the surface in contact with the NMP / water bath) was imaged as a selective surface morphology. Film samples were coated with a Crestington 208 high resolution sputter coater equipped with a thickness controller MTM-20, with a Pt / Pd target of about 0.3 nm. The surface morphology was imaged using a mode of in-lens surface high sensitivity detection at a magnification of 100,000, capable of low voltage (≦ 5 kV, probe current 200 nA). To assess the pore size distribution, a minimum of 3 images were combined and pooled for analysis for digital image analysis using Cremex Vision PE 6.0.35 software. Samples for cross-sectional imaging were immersed in ethanol for 5 minutes, cryomilled with liquid nitrogen, then left to reach room temperature and dried in air. Cryogenic film samples were coated with a Pt / Pd target and imaged using SEM for cross-sectional morphology.

  Water and membrane surface interactions were quantified by contact angle measurement using a Kruss DA-25 droplet shape analysis system. A small square section of the membrane was cut from the center of the membrane and affixed onto a microscope glass slide using double-sided tape. Two microliters of water droplets were placed on the surface, and the shape of the droplets was measured 5 times at 1 second intervals using digital curve fitting, and the contact angles obtained between the water droplets and the membrane surface were averaged.

Examples 9-10: Membranes Cast with 20/80 MPP-DMP Copolymer and PS-PEO Diblock Copolymer Samples of diblock amphiphilic block copolymers were obtained from Sigma-Aldrich, which The catalog states that it contains a block of polystyrene (PS) having a Mn of about 30,000 g / mol, which is linked to poly (ethylene oxide) (PEO) of about 1,000 g / mol Mn. Yes. From this description, we determine that this PS / PEO block copolymer contains only about 3 wt% hydrophilic blocks by weight. A poly (phenylene ether) copolymer was prepared by copolymerization of 2-methyl-6-phenylphenol (MPP) and 2,6-dimethylphenol (DMP). As used herein, the comonomer ratio of poly (phenylene ether) is a molar ratio. In Examples 9 and 10, solutions containing 16 wt% 20/80 MPP-DMP copolymer (Example 2) were prepared in the presence of 2 and 4 wt% PS / PEO diblock copolymer, respectively, and Following the same procedure, it was cast into a membrane. The results of SEM image analysis of these films are shown in FIG. The surface appearance of the film evaluated by SEM was found to be very similar to that of Example 6 prepared by casting only the MPP-DMP copolymer.

  The blends of Examples 9-10 containing PS / PEO copolymers are as good or better as those seen in Example 6 made from MPP-DMP copolymer alone with phase change casting. The result was a membrane surface with a pore size distribution indicating non-uniformity in the size distribution. From this, we can conclude that the presence of short blocks of PS did not substantially disturb the inherently good film-forming properties of MPP-DMP copolymers. The contact angle of membranes containing PS-PEO diblock as an additive is most likely caused by a slight tendency to decrease the contact angle and the creation of a miscible blend between the MPP-DMP copolymer and the PS block , Tg decrease. Since this type of additive is expected to be insoluble in NMP / water, as opposed to PVP, the additive can be expected to be present in the membrane itself.

  Given the low level of PEO in commercial PS / PEO diblock copolymer samples, it is not surprising that the contact angle of the membrane was only slightly reduced in the resulting blended membrane. In Examples 9 and 10, the PS-PEO block copolymer can be replaced with an amphiphilic block copolymer comprising a poly (phenylene ether) block or poly (phenylene ether) copolymer block and a hydrophilic block or graft.

Preparative Examples 11-13: Preparation of MPP-DMP Copolymers with 20, 50, and 80 mole percent MPP MPP-DMP copolymers with 20, 50, and 80 mole percent MPP were prepared as Preparative Examples 2-4. Prepared in a 1 gallon reactor using the same method. The dried copolymer was evaluated for molecular weight distribution as described above for Preparative Examples 2-4. The results of Preparative Examples 11-13 are summarized in Table 7. “Mn” represents a number average molecular weight, “Mw” represents a weight average molecular weight, “D” represents polydispersity, and “g” represents gram.

Examples 18-20 and Comparative Example 3: Hollow Fiber Spinning Test Membrane-forming compositions (NMP casting dopes) of Examples 14-16 (including the MPP-DMP copolymers of Examples 11-13, respectively), and Comparative Example 3 Were processed into hollow fiber membranes according to the method disclosed in the '848 application. ULTRASON ™ 6020P (BASF) was kept under vacuum for 24 hours to remove all moisture before mixing. The chemicals were mixed until a homogeneous solution was obtained. Prior to filling the spinning solution into the spinning facility, the composition was filtered through a 25 μm metal mesh to remove any residual particles in the composition. The spinning solution was degassed for 24 hours before spinning. For all spinnings, a 70 wt% deionized water and 30 wt% NMP bore solution was prepared and degassed for 24 hours prior to use.

  PES and PVP hollow fiber membranes (Comparative Example 3) were prepared on a laboratory scale by wet and dry immersion precipitation spinning under the conditions adapted from the '848 application, using the apparatus shown in the schematic diagram of FIG. It was. The copolymer solution along with the bore liquid was simultaneously pumped through the double orifice spinneret, passed through the air gap, and then drawn into the water condensation bath. The take-up speed was controlled by a pulling wheel, which also allowed for yarn drawing. An 18 wt% solution of MPP-DMP copolymer according to Example 12 in NMP was successfully spun into hollow PPE using the same equipment and conditions used to prepare Comparative Example 3, Example 18 was produced.

  A summary of yarn spinning conditions, spinneret geometry, and measured dimensions of the hollow fiber after drying is shown in Table 10. In Comparative Example 3, according to the example in the '848 application, the rinse bath was kept at 65 ° C., which is understood to be for removing excess PVP from the surface of the hollow fiber membrane. In Examples 18-20 (which were prepared from 20/80, 50/50, and 80/20 MPP-PPE copolymers, respectively), the wash-out bath was used for safety in yarn handling and Since there was no PVP to be washed away, it was kept at 30 ° C. The take-up speed was adjusted so that the wall thickness of the two hollow fiber samples was in the range of 40-60 micrometers. The post-treatment process for the manufactured hollow fiber was as described in the '848 application. The yarn was washed in purified water at 70 ° C. for 3 hours. After 1.5 hours, the water was changed. Later, the yarn was washed with water at the faucet temperature for an additional 24 hours. After the rinse step, the yarn was suspended in the laboratory at ambient temperature in air for drying.

  Based on the discovery that the viscosity of the film-forming polymer solution in NMP is very sensitive to the amount of MPP comonomer in the copolymer, the concentration of each resin is slightly above 3000 cP, essentially constant solution viscosity. Adjusted to produce. As a result, there is a direct correlation between the level of MPP comonomer in the copolymer and the mass of PPE per unit length of yarn, and Example 18a is the most efficient of resin under the same spinning conditions. Illustrate the use. The wall thickness of the yarn was also kept to a higher degree in Example 19, and further optimization of the yarn spinning conditions to reduce the wall thickness resulted in a greater reduction in mass per unit length. It suggested that it could be realized.

Preparation of Hollow Fiber Membrane Module A laboratory scale hollow fiber membrane module as shown in FIG. 2 was prepared for the measurement of purified water flux and fractional molecular weight as follows. Depending on the shape, 5-10 threads are passed through the polypropylene tube and t-connector, which provides access to the outer surface of the hollow fiber. Both ends were sealed with a thermal adhesive. After the adhesive solidified, the module was carefully cut open at one or both ends to expose the hollow fiber inner core and make the module ready for use. The membrane length was between 25 and 30 cm. The yarn of Example 20 was more brittle than the other yarns, and special care was needed to bond the yarn of Example 20 to the module to avoid damaging the yarn.

Measurement of purified water flux The purified water flux (CWF) was measured as follows. The pump was connected to a mass flow controller and a pressure sensor. After the pressure sensor, the membrane module was connected so that the filtration direction was internal pressure filtration, that is, water was pushed into the bore side of the membrane and permeated through the membrane to the outside of the membrane. The filtration system was dead-end filtration, ie only one end of the filtration module was cut open and connected to the feed solution. The flow rate was set at 100 g / h and the feed pressure was recorded over time. After pretreatment of the membrane module, the experiment was continued for 1 hour to achieve steady state conditions.
Prior to measurement, all hollow fibers were wetted with a mixture of 50 wt% water and 50 wt% ethanol. Thereafter, purified water was permeated through the hollow fiber membrane for 15 minutes to remove any residual ethanol from the yarn. The measurement was started immediately after the pretreatment.

Measurement of Fraction Molecular Weight Prior to measurement of Fraction Molecular Weight (MWCO), all membrane modules were wetted with a mixture of 50 wt% water and 50 wt% ethanol. Next, purified water was permeated through the hollow fiber membrane for 15 minutes to remove any residual ethanol from the yarn. The measurement was started immediately after the pretreatment.

  FIG. 5 shows a schematic diagram of the MWCO measuring apparatus. Both ends of the hollow fiber filtration module shown in FIG. 4 were cut, the feed solution was pumped through the interior of the hollow fiber, and the retentate was recirculated to the feed tank. The permeate solution was circulated through the outside of the yarn through a T-connector and recycled to another feed tank. The cross flow rate is controlled by a pump and the feed, retentate, and pressure are recorded. The permeate pressure was atmospheric pressure. A retentate side valve can optionally be used to control the retentate pressure.

Turbulence inside the hollow fiber is desirable to prevent concentration bias during the experiment. The crossflow velocity is targeted at a Reynolds number of about 3000 to create turbulence. The Reynolds number is defined according to Equation 1, where “η” is defined as the fluid dynamic coefficient, “ρ” is defined as the fluid density, and “v” is the fluid velocity. “D” is defined as the inner diameter of the yarn.
As feed solution, a mixture of 4 different dextrans with different molecular weights (1 kDa, 4 kDa, 8 kDa and 40 kDa) was used. The concentration of the feed solution was 0.5 g / L for each dextran. The fractional molecular weight is defined as the molecular weight of the chemical species retained by the membrane up to 90 percent. Retention is calculated by comparing gel permeation chromatography of the initial solution of dextran with that measured in the permeation and retention solutions after reaching equilibrium.

Example 19: Membrane Preparation According to the procedure described above, the membrane was combined with the amphiphilic polymer described herein (1-10 wt%) in 50/50 MPP-DMP copolymer of Example 12 ( 12-20 wt%) of the doped NMP solution to form an asymmetric membrane. The temperature was maintained at 35 ° C. throughout the casting and initial phase change setting process. The vial of polymer NMP solution is equilibrated for several hours with rolled aluminum “drive lock” controlled at 35.0 ± 0.1 ° C. by use of an electric heater. The glass casting plate and casting knife are allowed to equilibrate on an electrically heated hot plate at 35.0 ± 0.1 ° C. for several hours before use. 2 liters of coagulation solution of NMP / water is placed in a 35.0 ± 0.1 ° C. digital controlled thermostat. In addition, the viscosity of the NMP solution of the polymer is measured using a Brookfield LVDV3T viscometer equipped with cone and plate, thermometry and a circulating water bath, controlled within 0.1 ° C. from the desired temperature.

Example 20. Hollow fiber spinning The amphiphilic polymer described herein in combination with the hydrophobic polymer of Example 17 in a weight ratio of 12% to 20% is prepared according to the methods described in Example 18 and Comparative Example 3. Processed into a hollow fiber membrane.
The hollow fiber membrane module is prepared as described above, and the water flux is measured. The yarn is about 10 to about 80 L / (h · m ² · bar), or about 20 to about 80 L / (h · m ² · bar), or about 40 to about 60 L / (h · m ² · bar). CWF can be brought about.

  As used herein, including includes “consisting essentially of” and “consisting of”. In connection with describing the invention (especially in connection with the following claims), the terms “a” and “this” and similar directives are specifically referred to herein. Unless otherwise stated or clearly denied by the relevant part, it should be interpreted as including both singular and plural. “Or (or)” means “and / or”. The endpoints of all ranges that cover the same element or property are included in the range and can be combined independently. All ranges disclosed herein include endpoints that can be combined independently of each other. The terms “first”, “second”, etc. do not indicate any order, amount, or importance and are only used to distinguish one element from another.

  As used herein, the term “hydrocarbyl” refers to a group comprising carbon and hydrogen, optionally with 1 to 3 heteroatoms such as oxygen, nitrogen, halogen, silicon, sulfur, or combinations thereof. Widely represents a group having a linkage moiety to an outer atom. Unless otherwise specified, a hydrocarbyl group may be unsubstituted or substituted if the substitution does not significantly adversely affect synthesis, stability, or use of the compound. As used herein, the term “substituted” refers to nitrogen, oxygen, sulfur, halogen, provided that at least one hydrogen of the hydrocarbyl group does not exceed the normal valence of any atom. , Silicon, or a combination thereof. For example, when the substituent is oxo (ie, “═O”), two hydrogens on the specified atom are replaced by the oxo group. Combinations of substituents and / or variables are permissible provided that the substitutions do not significantly adversely affect synthesis, stability, or use of the compound.

  All patents, patent applications, and other references cited are hereby incorporated by reference in their entirety. However, if a term in this application contradicts or conflicts with an incorporated reference, the term according to this application takes precedence over the conflicting term with an incorporated reference.

  While exemplary embodiments have been described for purposes of illustration, the above description should not be considered limiting to the scope of the invention. Accordingly, various modifications, adaptations, and alternatives may occur to those skilled in the art without departing from the spirit and scope of the present invention.

Claims (20)

A hydrophobic block comprising, consisting essentially of, or consisting of a poly (phenylene ether) block or a poly (phenylene ether) copolymer block; and a hydrophilic block or graft;
An amphiphilic block copolymer characterized by comprising:   The amphiphilic block copolymer of claim 1 comprising 20 to 50 weight percent of the hydrophobic block and 50 to 80 weight percent of the hydrophilic block or graft. Copolymer. The amphiphilic block copolymer according to claim 2, wherein the hydrophobic block has a repeating unit having the following structure:
Poly (phenylene ether) having
Wherein each time Z ¹ appears, it is independently halogen, unsubstituted or substituted C _1-12 hydrocarbyl (provided that the hydrocarbyl group is not a tertiary hydrocarbyl), C _1-12 hydrocarbylthio, C _{1. 12} hydrocarbyloxy or C _{2 to 12} halohydrocarbyloxy (wherein at least two carbon atoms separate the halogen and oxygen atoms), be; Z ² is each appear, independently, hydrogen, halogen, Unsubstituted or substituted C _1-12 hydrocarbyl (provided that the hydrocarbyl group is not a tertiary hydrocarbyl), C _1-12 hydrocarbylthio, C _1-12 hydrocarbyloxy, or C _2-12 halohydrocarbyloxy (here And at least two carbon atoms separate the halogen and oxygen atoms) An amphiphilic block copolymer characterized by being: The amphiphilic block copolymer according to any one of claims 1 to 3, wherein the hydrophobic block is
100 to 20 mole percent of repeating units derived from 2,6-dimethylphenol; and
The following structure:
From 0 to 80 mole percent of repeating units derived from a second monohydric phenol having:
Comprising a poly (phenylene ether) copolymer, wherein Z is C _1-12 alkyl or cycloalkyl, or the following structure:
Wherein q is 0 or 1, and R ¹ and R ² are independently hydrogen or C _1-6 alkyl;
All mole percentages are relative to the total moles of all repeat units;
The poly (phenylene ether) copolymer block has an intrinsic viscosity of 0.1 to 0.5 deciliter / gram measured in chloroform at 25 ° C .;
An amphiphilic block copolymer characterized by: The amphiphilic block copolymer according to any one of claims 1 to 4, wherein the hydrophobic block of the amphiphilic copolymer is:
80 to 20 mole percent of repeating units derived from 2,6-dimethylphenol; and
20 to 80 mole percent of repeating units derived from the second monohydric phenol;
An amphiphilic block copolymer comprising a poly (phenylene ether) copolymer comprising   The amphiphilic block copolymer according to claim 5, wherein the second monohydric phenol contains 2-methyl-6-phenylphenol.   The amphiphilic block copolymer according to any one of claims 1 to 6, wherein the hydrophilic block or graft contains a polymerized hydrophilic ethylenically unsaturated monomer. Copolymer.   8. The amphiphilic block copolymer according to claim 7, wherein the hydrophilic ethylenically unsaturated monomer is a terminal methoxylated poly (ethylene oxide) methacrylate, 4-vinylpyridine, N-vinylpyrrolidone, N, N-dimethylacrylamide. , 4-acryloylmorpholine, or a combination comprising at least one of these, an amphiphilic block copolymer.   Polymerization of hydrophilic ethylenically unsaturated monomers in the presence of hydrophobic polymers comprising, consisting essentially of, or consisting of poly (phenylene ether) or poly (phenylene ether) copolymers to produce amphiphilic block copolymers A process for producing an amphiphilic block copolymer.   The method according to claim 9, wherein the polymerization is controlled radical polymerization.   11. The method according to claim 10, wherein the controlled radical polymerization is atom transfer radical polymerization, reversible addition-cleavage transfer polymerization, or stable free radical polymerization.   The method according to claim 9, wherein the polymerization is graft polymerization.   13. The method according to any one of claims 9 to 12, wherein the hydrophilic ethylenically unsaturated monomer is a terminal methoxylated poly (ethylene oxide) methacrylate, 4-vinylpyridine, vinylpyrrolidone, N, N-dimethyl. A method comprising acrylamide, 4-acryloylmorpholine, or a combination comprising at least one of these. A hydrophobic polymer comprising, consisting essentially of, or consisting of a poly (phenylene ether) or poly (phenylene ether) copolymer; and a hydrophobic block comprising a poly (phenylene ether) block or a poly (phenylene ether) copolymer block;
An amphiphilic block copolymer comprising a hydrophilic block or graft;
A porous asymmetric membrane characterized in that it comprises, consists essentially of, or consists of. A hydrophobic polymer comprising, consisting essentially of, or consisting of poly (phenylene ether) or poly (phenylene ether) copolymer;
An amphiphilic block copolymer comprising a hydrophobic block comprising a poly (phenylene ether) block or a poly (phenylene ether) copolymer block and a hydrophilic block or graft; and a water miscible polar aprotic solvent;
Comprising, consisting essentially of, or consisting of,
A porous asymmetric film-forming composition, wherein the hydrophobic polymer and the amphiphilic block copolymer are dissolved in the water-miscible polar aprotic solvent. A method of forming a porous asymmetric membrane, comprising:
A hydrophobic polymer comprising, consisting essentially of or consisting of a poly (phenylene ether) or poly (phenylene ether) copolymer, and a hydrophobic block comprising poly (phenylene ether) or poly (phenylene ether) copolymer;
Dissolving an amphiphilic block copolymer comprising a hydrophilic block or graft in a water miscible polar aprotic solvent to produce a porous asymmetric membrane-forming composition;
Phase-transforming said porous asymmetric membrane forming composition in a first non-solvent to form a porous asymmetric membrane;
Optionally washing the porous asymmetric membrane in a second non-solvent; and optionally drying the porous asymmetric membrane to produce the porous asymmetric membrane;
A method comprising the steps of: 17. The porous asymmetric membrane, composition or method according to any one of claims 14 to 16, wherein the hydrophobic polymer has a repeating unit having the structure:
Poly (phenylene ether) having
Wherein each time Z ¹ appears, it is independently halogen, unsubstituted or substituted C _1-12 hydrocarbyl (provided that the hydrocarbyl group is not a tertiary hydrocarbyl), C _1-12 hydrocarbylthio, C _{1. 12} hydrocarbyloxy or C _{2 to 12} halohydrocarbyloxy (wherein at least two carbon atoms separate the halogen and oxygen atoms), be; Z ² is each appear, independently, hydrogen, halogen, Unsubstituted or substituted C _1-12 hydrocarbyl (provided that the hydrocarbyl group is not a tertiary hydrocarbyl), C _1-12 hydrocarbylthio, C _1-12 hydrocarbyloxy, or C _2-12 halohydrocarbyloxy (here And at least two carbon atoms separate the halogen and oxygen atoms) A porous asymmetric membrane, composition or method, characterized in that The porous asymmetric membrane, composition or method according to any one of claims 14 to 17, wherein the hydrophobic polymer is
100 to 20 mole percent of repeating units derived from 2,6-dimethylphenol; and
The following structure:
From 0 to 80 mole percent of repeating units derived from a second monohydric phenol having:
Comprising a poly (phenylene ether) copolymer, wherein Z is C _1-12 alkyl or cycloalkyl, or the following structure:
Wherein q is 0 or 1, and R ¹ and R ² are independently hydrogen or C _1-6 alkyl;
All mole percentages are relative to the total moles of all repeat units;
The poly (phenylene ether) copolymer has an intrinsic viscosity of 0.7 to 1.5 deciliters / gram measured in chloroform at 25 ° C .;
A porous asymmetric membrane, composition, or method.   19. The porous asymmetric membrane, composition or method according to any one of claims 14 to 18, wherein the hydrophobic polymer is 80 to 20 mole percent repeating units derived from 2,6-dimethylphenol. And a poly (phenylene ether) copolymer comprising 20 to 80 mole percent of repeating units derived from said second monohydric phenol; and a porous asymmetric membrane, composition or method.   The porous asymmetric membrane, composition or method according to claim 19, wherein the second monohydric phenol comprises 2-methyl-6-phenylphenol. Thing or method.